Next Article in Journal
Fine-Tuning of Polymeric Resins and their Interfaces with Amorphous Calcium Phosphate. A Strategy for Designing Effective Remineralizing Dental Composites
Next Article in Special Issue
New Biocompatible Polyesters Derived from α-Amino Acids: Hydrolytic Degradation Behavior
Previous Article in Journal / Special Issue
Diasteromeric Effect on the Homolysis of the C–ON Bond in Alkoxyamines: A DFT Investigation of 1,3-Diphenylbutyl-TEMPO
Article Menu

Export Article

Open AccessArticle
Polymers 2010, 2(4), 364-377; doi:10.3390/polym2040364

Chemically Induced Dynamic Nuclear Polarization during the Thermolysis of Alkoxyamines: A New Approach to Detect the Occurrence of H-Transfer Reactions

1
Physical Chemistry Department, Novosibirsk State University, Novosibirsk, Russia
2
International Tomography Center SB RAS, Novosibirsk, Russia
3
UMR 6264-LCP, CNRS-Aix-Marseille Université, , case 521, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
*
Authors to whom correspondence should be addressed.
Received: 30 August 2010 / Revised: 23 September 2010 / Accepted: 26 September 2010 / Published: 28 September 2010
(This article belongs to the Special Issue Advanced Polymer Architectures)
View Full-Text   |   Download PDF [1000 KB, 29 September 2010; original version 28 September 2010]   |  

Abstract

Thermal decomposition of alkoxyamines in the presence of scavengers was found to proceed with the formation of chemically induced nuclear polarization detected by 1H NMR. The distinctive Chemically Induced Dynamic Nuclear Polarization (CIDNP) features were studied using the example of three alkoxyamines: 4-nitrophenyl 2-(2,2,6,6-tetramethylpiperidin-1-yloxy)-2-methylpropanoate (1a), 4-nitrophenyl 2-(2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxy)-2-methylpropanoate (2a) and 4-nitrophenyl 2-(2,2,5,5-tetramethyl-4-phenyl-2H-imidazol-1-oxy)-2-methylpropanoate (3a) in the presence of PhSH. The analysis of CIDNP signs of methacrylate protons allows us to conclude on the occurrence of hydrogen atom transfer reaction in geminate radical pair formed in alkoxyamine thermolysis. Thus, CIDNP is a fast and sensitive method to detect the occurrence of intra/intermolecular hydrogen transfer in alkoxyamine thermolysis.
Keywords: nitroxide mediated polymerization; alkoxyamines; H-transfer reactions; CIDNP nitroxide mediated polymerization; alkoxyamines; H-transfer reactions; CIDNP
Figures

This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Edeleva, M.; Marque, S.R.A.; Bertin, D.; Gigmes, D.; Guillaneuf, Y.; Bagryanskaya, E. Chemically Induced Dynamic Nuclear Polarization during the Thermolysis of Alkoxyamines: A New Approach to Detect the Occurrence of H-Transfer Reactions. Polymers 2010, 2, 364-377.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Polymers EISSN 2073-4360 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top